Method of cracking oils



J. c. BLACK METHOD OF CRACKING OILS May 19, 1931.

Filed Nov. 14, 1928 ATTORN EY .Patented May 19, 1931 UNITED STATES y,PATlszNT OFFICEl 'JOHN C. BLACK, OFLOS ANGJEIJIEIS, CALIFORNIA imrnon or einem@ oILsj l Application led November 14, 1928. Serial No. 319,396.

tains a higher percentage of non-detonating carbocyclic hydrocarbons than is usually obtained bythe well-known thermocracking processes for the production of motor fuels.

This application is a continuation in part of the a plication of John C. Black, Serial A No. 148, 34 filed Nov. 16, 1926, now Patent No. 1,770,098, for method of'cracking oil, in which a process is described for cracking petroleum oils at thermocracliing temperatures in the presence of anhydrous aluminum 2o chloride and under a pressure sufficient to prevent any substantial vaporization thereof. This application is an improvement thereto, in that the metallic halide employed is caused to combine with'the unsaturated hydrocarbons contained in a petroleum oil,

is separated froml the saturated hydrocarbons and is thereafter decomposed into gasoline stock and higher boiling hydrocarbons by the application of heat in a separate con- 3o tainer, while the separated saturated hydrocarbons are subjected to a thermocracliing operation, preferably under a presure suicient to prevent any substantial vaporization thereof. Y

An object of the invention is to produce gasoline boiling point stock or motor fuel suitable for use in internal combustion engines with a high compression ratio.

Another object of the invention is to pro- 40 duce a motor fuel Vsuitable for usein internal combustion engines with a high'compression ratio without requiring the use of anti-knock compounds, `such as tetraethyl lead.

Another object of the invention is to provide a continuous process for converting petroleum oils into gasoline boiling point stock, in which a petroleum oil mixed with the rerliisite amount of an anhydrous metallic ha de, preferably iron or aluminum chlo-L ride,is caused to flow into a reaction chamber and -be commingled therein with a hot petroleumoil distillate continuously produced from the cracking and fractionation of lthe saturated hydrocarbons separated in the process; continuously separating the unsaturated hydrocarbons combined with the s'aid anhydrous metallic halide from the saturated hydrocarbons continuously decomposing the said unsaturated hydrocarbons combined with the anhydrous metallic halide by the application of heat in a separate container, into gasoline boiling point hydrocar-5 bons and passing the same mto a fractionating tower; continuously passing the. said separated `Saturated hydrocarbons through a heater coil maintained under super-atmospheric pressure and at' a' thermocracking temperature separating, condensin and collecting the gasoline stock produce by the said thermocracking of the saturated hydrocarbons and from the thermocatalytic decomposition of theunsaturated hydrocarbons combined with the said anhydrous metallic halide, and continuously returning the separated hot higher boiling distillate from the fractionating operation into the said reaction chamber.

Various other objects and advantages of l'the present invention will'be apparent from the description of the preferred form or example of thel process embodying the inventank for holding the petroleum oil to be trea'ted. Pipe 2,-contro lled by the valve 85', connects the inlet'side of pump 3 to tank 1. Pipe Y i 95' 2 connects the discharge side of pump 3 with heat exchanger 4. fi'sa pipe connectlng heat exchanger 4 with heater coil 90 stationed in the'furnace 89. The furnace 89 is provided with a burner 88;l Pipe 87 connects the heater'coil 99 to fractionating tower 6.- 7 lis a continuously fractionating,

j tion. For this purpose, reference is made to vapor pipe which connects fractionating tower 6 to condenser coil 8. Condenser coil 8 is stationed in the condenser box 60. Pipe 85 connects the condenser coil 8 to look-box 9. The look-box 9 is connected by a pipe 86 to tank 10. 11 is a pipe controlled by a valvel 11, connecting fractionating tower'6 with tank 12. 13 isI a feed hopper connected to tank 12. 14 is a pipe controlled by valve 14 which connects the metallic halide tank 15 to the feed hopper 13. 16 is a pipe controlled by a valve 16 which connects tank 12 with pump 17. 18 is a pipe controlled by the valve 18 which connects pump 17 to a mixer 64. The mixer 64 is connected to reaction chamber 47 ending in a spray pipe 18". The reaction chamber 47 is provided with a separator plate 54, a gauge glass 56, a liquid level controlling device 55 and a pipe 53 which connects the upper portion of the reaction chamber 47 with the lower portion. 52 is a pan stationed in the upper portion of the reaction chamber 47. Pipe 49 connects the reaction chamber 47 at the top to the lower section of fractionating tower 31. Pipe l58 controlled by valve 58 connects the bottom section of reaction chamber 47 to still 57. The still 57 is provided with a burner 61 situated in a furnace 61. A pipe 57 controlled.

by valve 80 is connected to the bottom of still 57 and leads to a source of storage not shown. Va or pipe 67 connects the dome of still 57 to the upper section of fractionating tower 31. Pipe 51, controlled by valve 51 connects the reaction chamber 47 to the inlet side of pump 19. Pipe 50 controlled by valve 78 connects the discharge side of pump 19 to heat exchanger 20. Pipe 21 connects heat exchanger 20 to pipe 22. Pipe 22 controlled by valve 22 connects pipe 50 to heating coil 23. The heating coil 23 is stationed in the furnace 24 and is provided with a burner 62. Pipe 25 connects the heater coil 23 at the top to the lower section of heater coil 27. The heater coil 27 is stationed in the upper section of furnace 26'and is provided with a burner 63. Pipe 28 connects .the heater coil 27 at the top to heat exchanger 20. Pipe 29, controlled by a pressure regulating and discharge valve 29 connects the heat exchanger 2O to the lower section of fractionating tower 31. A pressure gauge 30 is connected to the pipe 29. The fractionating tower 31 is provided with a separator plate 33, bubble caps 32 and 34, and a dephlegmator 37. Pipe 38 connects the dephlegmator 37 at the top to condenser coil l39. The condenser coil 39 is stationed in the condenser box 59. A pipe 59 connects the condenser coil 39 to look-box40. A vapor vent pipe 41 is connected to the top of lookbox 40 and leads to an absorber not shown. Pipe 42 connects the look-box 40 to a naphtha tank 43. A pipe 81 controlled by the valve 81 is connected to the naphtha tank 43 near the bottom and leads to a source of storage not shown. Pipe 44 controlled by valve 44 connects fractlonating tower 31 at the bottom to heat exchanger 4. Pipe 45 connects the heat exchanger 4 to the inlet side of pump 46. Pipe controlled by valve 65 connects the discharge side of pump 46 to residual oil tank 47 Pipe 82, controlled by the valve 82 is connected to the residual oil tank 47 at the bottom and leads to a source of storage not shown. Pipe 36 controlled by the valve 36 connects the pipe 50 to fractionating tower 31 near the top. Pipe 35 connects the fractionating tower 31 just above the separator plate 33 to a cooling coil 66. The cooling coil 66 is stationed in the cooling box 65 and is connected to the mixer 64, by a pipe 83 controlled by a valve 35.

The preferred process as carried out with the\apparatus just described is as follows:

Petroleum oil or a petroleum oil distillate such as gas oil stock, contained in the petroleum oil tank 1, is permitted to flow through pipe 2 and into kthe suction side of pump 3, the flow being regulated by operating valve 85. Pump 3 discharges the petroleum oil distillate through pipe 2, heat exchanger 4, pipe 5 and then through heater coil 90 which is stationed in the upper section of furnace 89. A burner 88 is stationed in the lower part' of furnace 89 and so regulated that the oil passing through the heater coil 90 will attain a temperature above the boiling point of water, so that the oil passing out of fractionatin tower 6 will be completely dehydrated. Prefrably the oil is maintained at a ternperature of 230 to 300 degrees F. From the heater coil 90 the hot oil passes through pipe 87 and into fractionating tower 6 where all Water and any low boiling hydrocarbons are vaporized and separated from the higher boiling oils. The vaporized water and low boiling hydrocarbons pass from the top of fractionating tower 6 through pipe 7 and are condensed to a liquid on passing through the condenser coil 8. From condenser coil 8, the separated condensed water and lower boiling hydrocarbons flow through pipe 85, look box 9, pipe 86 and are collected in tank 10. From tank 10, the lower boiling hydrocarbons and water may be conducted to a water separator not shown, the water separated and the lower boiling hydrocarbons employed for gasoline stock or for other purposes known in the art. y

The dehydrated higher boiling oils pass from the bottom of fractionating tower 6 through pipe 11 and into tank 12, the flow being regulated by operating valve 11 A comminuted metallic halide, such as anhydrous aluminum chloride or ferric chloride, commingled with a water-free petroleum oil in quantities suiiicient to render the same through ipe 14 into feed hopper 13 which is connected) to the said tank 12. The quantity of anhydrous metallic -halide introduced ranges-from approximately 1/4. to 2 pounds per gallon of petroleum oil to be treated, this quantity depending upon the petroleum oil stock to be treated and the products desired. The greater the percentage of metallic halide employed, the' greater will be the percentage of lower boiling hydrocarbons produced. From tank 12 the petroleum oil -mixed with metallic halide, passes through pipe 16 into the suction side of pump 17, the flow being controlled by regulating valve 16. Pump 17 discharges the oil and metallic halide through pipe `18 .and into the mixer 64, valve 18 being open. In the mixer 64 the petroleum oil and metallic halide is continuously commingled with the higherboiling oil separated in the fractionating tower 31, which passes from said fractionating tower 31 through pipe 35, cooling coil 66, pipe 83 and then into said mixer 64, the How being controlled by valve 35. The temperature of the oil passing into the mixer 64 is controlled by passing water or other cooling uid through a cooler box 65, the temperature being so regulated that the commingled mixture of oil and metallic halide passing out of the mixer 64 will not exceed 300 degrees F., preferably a temperature of approximately 150 to 300 degrees F. is maintained. The commingled mixture of petroleum oil and metallic halide at a temperature of approximately '150 to 300 degrees F. passes into the reaction chamber 47 and then through the pipe 53 which is connected to the lower section of said reaction chamber 47 ,where the metallic halide combined with the unsaturated hydrocarbons contained in the petroleum oil are continuously .separated from the saturated hydrocarbons by gravity and pass into still 57 through the pipe 58, the flow being controlled by operating valve 58, maintaining a denite level of the combined unsaturated hydrocarbons and metallic halide in the said lower section of the reaction chamber 47, observing the level in gauge glass 56. In still 57 the metallic halide combined with the unsaturated `hydrocarbons are heated to a decomposing temperature ranging from approximately 300 to 500 degrees F., whereby the unsaturated hydrocarbons are catalytically converted into hydrocarbons of the carbocyclic series. These carbocyclic hydrocarbons pass out of the still 57 into vapor pipe 67 and then into fractionating tower 31 where the gasoline stock is separated from the higher boiling hydrocaro bons together with the' gasoline stock produced by a thermocracking operation of the higher boiling saturated hydrocarbons.

The saturated hydrocarbonsseparated in the reaction chamber 47 are continuously permitted to iow into the suction side of pump 19, this How being regulated by a liquid level control 554and valve 51'. 19 discharges the separated saturated hy rocarbon `oil under=a pressure of approximately 1000 `'exchanger 420. From pipe 22 the oil passes through heater coil 23 under a pressure o approximately 1000 pounds where the temperature of the oil is raised to a cracking temperature of approximately 750 to 850 degrees F.,

or higher, by the burner 62. From heater coil 23 the hotoil at the said cracking temper-l ature passes through pipe 25 and then through heater coil 27 wherein the temperature is maintained at the said cracking temperature of 750 to 850 degrees F., or"higher, bythe burner 63. From heater coil 27 the hot cracked oil passes through pipe 28, heat exchanger 20, pipe 29 and then through a pressure regulating and discharge valve 29 where the pressure is reduced to approximately atmospheric. From pipe 29 the hot cracked oil passes into the lower section offractionating tower 31 wherein the gasoline stock produced by the thermocracking operation, together with the gasoline stock produced by the said metallic halide catalytic decomposition reaction, are separated from .the higher boiling hydrocarbons passing through the dephlegmator 37, pipe 38 and then through condenser coil 39 where the gasoline stock is condensed. From the condenser coil 39 theI condensed gasoline stock passes through pipe 59', look box 40, pipe 42 and is collected in the naphtha tank 43. From the naphtha tank 43, the gasoline stock or naphtha may be conducted to a storage not shown byvmeans of pipe 81 controlled by valve 81. The uncondensed gaseous products roduced in the process are separated in loo box 40 and are conducted rinto a pipe 41 which leads to an absorber, not shown, whereby the dissolved and entrained gasolinestock is separated from the permanent gaseous products and returned to the gasoline stock- The residual oil separated in the lower section'of fractionating tower 31 passes out through the pipe 44, the flow being regulated by valve 44. From pi e 44 the residual oil passes through heat exc anger 4, pipe 45 and then into the suction side of pump 46. Pump 46 discharges the said residual oil through pipe 65 and into residual oil tank 47. From tank 47 the residual oil may be conducted to a 'storage not shown by4 a Apipe separator plate 33, passes out through the pipe 35 and is conducted through a cooling coil 66 stationed in the cooler box 65. The cooler box is provided with inlet and outlet means for passing a cooling fluid such as water, over the cooling coil 66, the temperature of the distillate being regulated to such a degree that the temperature of the mixed oils entering the reaction chamber 47 will be approximately 150 to 300 degrees F., so that a decomposition temperature of the metallic halide combined with the unsaturated hydrocarbons Will not take place. From cooling coil 66, the distillate cooled to the required degree passes through pipe 83 and into the mixer 64 and is commingled therein with the petroleum oil and metallic halide coming through the pipe 18 as heretofore described.

Vhile the process herein described is well adapted for carrying out the objects of the present invention, it is to be understood that Various changes and modifications may be made without departing from the spirit of the invention, and the invent-ion includes all such modifications and changes as come Within the scope of the appended claims.

What I claim is:

l. A process of producing gasoline boiling point hydrocarbons from higher boiling hydrocarbon oils, comprising, commingling petroleum oil with an anhydrous metallic halide suspended in petroleum oil at a temperature not. greater than 300 degrees F., separating from the other products of the reaction, oil composed substantially of saturated hydrocarbons, subjecting the saturated hydrocarbons to t-hermocracking conditions by the application of heat under superatmospheric pressure to produce by thermomolecular decomposition, gasoline boiling point hydrocarbons, and higher boiling oils, separately separating by fractionation and condensation, the gasoline boiling point hydrocarbons and a higher'boiling distillate containing unsaturated hydrocarbons from a residual oil, continuously cooling the said separated higher boiling distillate containing unsaturated hydrocarbons, to a temperature not in excess of 300 degrees F. and commingling the same with the said petroleum oil containing the anhydrous metallic halide to be again processed.

2. A process of producing asoline boiling point hydrocarbons from hig er boilingV hydrocarbon oils, comprising, commingling petroleum oil with an anhydrous metallichalide suspended in a petroleum oil at a temperature not greater than 300 degrees F., separating from the other products of the reaction, oil composed substantially of saturated hydrocarbons, subjecting the saturated hydrocarbons to thermocracking conditions by the application of heat under super-atmospheric pressure to produce by thermomolecular decomposition gasoline 'boiling point hydrocarbons and higher boiling oils, separately separating by fractionation and condensation, the gasoline boiling point hydrocarbons and a higher boiling distillate containing unsaturatedv hydrocarbons, from a residual oil, continuously introducing the higher boiling distillate as produced at a temperature substantially not above 300 degrees F. into the said commingled mixture of petroleum oil and metallic halide, to be again processed, continuously withdrawing the Inetallic halide products of reaction into a still and subjecting the same to a decomposing temperature to produce gasoline boiling point hydrocarbons along with higher boiling oils, and separating by fractionation the gasoline boiling point hydrocarbons along with the gasoline boiling point hydrocarbons produced by the said thermocracking of the saturated hydrocarbon oils.

3. A process of producing lower boiling hydrocarbons from higher boiling hydrocarbons, comprising, commingling an anhydrous metallic halide mixed with petroleum oil, with a petroleum oil distillate at a temperature of approximately 150-300-degrees F., to produce substantially saturated hydrocarbon oils and to fonm metallic halide reaction products with the unsaturated hydrocarbon oils contained in the petroleum oil and the petroleum oil distillate, said petroleum oil distillate bein continuously separated in the process by ractional condensation of cracked petroleum oil vapors produced by subjecting the substantially saturated hydrocarbon oils to' thermocracking conditions under super-atmospheric pressure at a temperature of approximately 750 to 850 degrees F. to produce gasoline boiling point hydrocarbons and higher boiling oils, and hydrocarbon oil vapors produced from a thermodecomposition of the metallic halide reaction products; continuously separating the substantially saturated hydrocarbons from the other products of the reaction, cracking the saturated hydrocarbons and separately separating by fractionation and condensation, the gasoline boiling point hydrocarbons together with gasoline boiling point hydrocarons produced from the said thermodecomposition of the metallic halide reaction products and the said petroleum oil distillate, from a residual oil, substantially as described.

4. A process of producing lower boiling hydrocarbons from higher4 boiling hydrocarbon oils, comprising, treating a higher boiling petroleum oil distillate derived from a cracked petroleum oil which is mixed with a hydrocarbon oil distillate subsequently produced in the process, with an uncracked petroleum oil commingled with an anhydrous metallic halide, at temperatures of approximately 150 t'o 300 degrees F., to produce an oil composed substantially of saturated hydrocarbons by chemical combination of the metallic halide with the unsaturated hydrocarbons contained in the said distillates and uncracked petroleum oil, separating the metallic halide reaction products from the saturated hydrocarbons, subjecting the separated saturated hydrocarbons to thermocracking conditions to crack the said saturated hydrocarbons, separately separating by fractionation and condensation, gasoline boiling point stock, a higher boiling distillate and a residual oil from the said cracked oil; subjecting the said separated metallic halide reaction products to a decomposing distillation operation to produce asoline boiling point .hydrocarbons and hig er boiling oils, separating by fractionation, the gasoline boiling point stock produced by said distillation of the metallic halide reaction products in a fractionating tower together with the gasoline stock produced in the cracking oper-4 ation. i

5. A process of producing gasoline boiling point hydrocarbons from hlgher boiling hydrocarbon oils, comprising, continuously commingling a higher boiling petroleum oil and a higher boiling petroleum oil distillate with an anhydrous metallic halide suspended in higher boiling petroleum oil, at a tempera;- ture of approximately 150 to l300 degrees F. to produce an oil composed substantlally of lsaturated hydrocarbons. and metallic halide reaction products by. chemical combination v of the anhydrous metallic halide with the unsaturated hydrocarbons contained in the petroleum oil and the petroleum oil distillate, said higher boiling petroleum oil distillate being continuously produced by a fractional condensation operatlon of cracked petroleum oil vapors, continuously produced by subjecting the, saturated hydrocarbons to thermocracking conditions to crack the saturated hydrocarbons separated in the process, mixed with a higher boiling distillate fractionally separated from the oil vapors produced by a distillation operation of the metallic halide reaction products, continuously separating the saturated hydrocarbons from the metallic halide reaction products and continuousl subjecting the metallic halide reaction prot?I ucts to a decomposing distillation operation A to produce gasoline boiling point hydrocarbons and higher boiling oils, and continuously separating by'fractionation and condensation the gasoline stock produced by said distillation of the metallic halide reaction` products together with gasoline stock prouced in the cracking operation.

6. A process of producing gasoline from higher boiling petroleum oils, comprising, extracting unsaturated hydrocarbons from higher boiling petroleum oils, by'treating the same with an anhydrous metallic halide grees F. to produce saturated hydrocarbons and metallic halide reaction products by chemical combination of the metallic halide with the unsaturated hydrocarbons contained commingled with\a petroleum oil, at temperatures of approximately 150 to 300 de- 

